G2 PREDICTION OF THE ENTHALPIES OF FORMATION FOR SOME DIATOMIC CATIONS AND NEUTRALS

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Densities and mixing volumes of mixtures of fluorobenzene, α,α,α-trifluorotoluene, tert-butylmethyl ether, and ethanol at temperature 298.15 K and pressure 0.1 MPa

The volumetric properties were evaluated from density data for the binary mixtures of (fluorobenzene + tert-butylmethyl ether), (α,α,α-trifluorotoluene + tert-butylmethyl ether), (tert-butylmethyl ether + ethanol), and the ternary mixtures of (fluorobenzene + tert-butylmethyl ether + ethanol) and (α,α,α-trifluorotoluene + tert-butylmethyl ether + ethanol). The observed densities were obtained by means of a vibrating-tube densimeter at the temperature 298.15 K and the pressure 101 kPa.The excess molar volumes of the ternary mixtures were estimated from binary solution data using several empirical equations with mean standard deviation less than 0.03 cm³·mol^-1. Stable chemical cross-associations among the molecules forming the mixtures were revealed.     

Multivariate Cramér-Rao inequality for prediction and efficient predictors

We derive and discuss a matricial Cramér-Rao type inequality for the quadratic prediction error matrix. A study of the attainment of the bound follows. Then we introduce an unbiased predictor for a bivariate Poisson process and prove that it is efficient, i.e. its quadratic error attains the Cramér-Rao bound.     

Predicting O-glycosylation sites in mammalian proteins by using SVMs

O-glycosylation is one of the most important, frequent and complex post-translational modifications. This modification can activate and affect protein functions. Here, we present three support vector machines models based on physical properties, 0/1 system, and the system combining the above two features. The prediction accuracies of the three models have reached 0.82, 0.85 and 0.85, respectively. The accuracies of the three SVMs methods were evaluated by 'leave-one-out' cross validation. This approach provides a useful tool to help identify the O-glycosylation sites in mammalian proteins. An online prediction web server is available at http://www.biosino.org/Oglyc.     

Chromatographic retention prediction and octanol-water partition coefficient determination of monobasic weak acidic compounds in ion-suppression reversed-phase liquid chromatography using acids as ion-suppressors

Although simple acids, replacing buffers, have been widely applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography (RPLC), none of the previously reported works focused on the systematic studies about the retention behavior of the acidic solutes in this ion-suppression RPLC mode. The subject of this paper was therefore to investigate the retention behavior of monobasic weak acidic compounds using acetic, perchloric and phosphoric acids as the ion-suppressors. The apparent octanol-water partition coefficient (K^″ow) was proposed to calibrate the octanol-water partition coefficient (Kow) of these weak acidic compounds, which resulted in a better linear correlation with log kw, the logarithm of the hypothetical retention factor corresponding to neat aqueous fraction of hydroorganic mobile phase. This log K^″ow−log kw linear correlation was successfully validated by the results of monocarboxylic acids and monohydrating phenols, and moreover by the results under diverse experimental conditions for the same solutes. This straightforward relationship not only can be used to effectively predict the retention values of weak acidic solutes combined with Snyder-Soczewinski equation, but also can offer a promising medium for directly measuring Kow data of these compounds via Collander equation. In addition, the influence of the different ion-suppressors on the retention of weak acidic compounds was also compared in this RPLC mode.     

Prediction of soil organic carbon partition coefficients by soil column liquid chromatography

To avoid the limitation of the widely used prediction methods of soil organic carbon partition coefficients (KOC) from hydrophobic parameters, e.g., the n-octanol/water partition coefficients (KOW) and the reversed phase high performance liquid chromatographic (RP-HPLC) retention factors, the soil column liquid chromatographic (SCLC) method was developed for KOC prediction. The real soils were used as the packing materials of RP-HPLC columns, and the correlations between the retention factors of organic compounds on soil columns (ksoil) and KOC measured by batch equilibrium method were studied. Good correlations were achieved between ksoil and KOC for three types of soils with different properties. All the square of the correlation coefficients (R2) of the linear regression between log ksoil and log KOC were higher than 0.89 with standard deviations of less than 0.21. In addition, the prediction of KOC from KOW and the RP-HPLC retention factors on cyanopropyl (CN) stationary phase (kCN) was comparatively evaluated for the three types of soils. The results show that the prediction of KOC from kCN and KOW is only applicable to some specific types of soils. The results obtained in the present study proved that the SCLC method is appropriate for the KOC prediction for different types of soils, however the applicability of using hydrophobic parameters to predict KOC largely depends on the properties of soil concerned.     

Peak recognition technique by a computer program copying the human judgement

Summary It is still difficult to determine peaks and peak boundaries properly, though peak recognition is very important for the precision of quantitative data. A new computer program overcomes these problems using a method which is adapted from human judgements. The algorithm was developed for HPLC but can also be used in other fields of analytical chemistry.     

Separation of mixtures of solvents with wide bore capillary columns connected in series

The gas chromatographic separation of the components of a complex mixture of industrial solvents, not possible on a single stationary phase owing to coelution of some of the compounds, has been achieved on two serially connected wide bore capillary columns of different polarity. The analysis of a mixture of twenty five compounds was optimized using the serial gas chromatography theory of Purnell and Williams. The capacity factors of sample components measured with the two columns coupled in series were found to agree with those predicted by theory, regardless of the order in which they were connected.     

A simplified integral equation for adsorption of gas mixtures on heterogeneous surfaces

Summary The multiple integral representing the overall isotherm for adsorption of gas mixtures on heterogeneous surfaces is transformed to a single integral, which is promising for predicting the mixed-gas adsorption by means of single-gas adsorption parameters. This transformation is possible when the adsorption energies of components for various adsorption sites show a certain type of correlation.

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Eine vereinfachte Integralgleichung für die Adsorption von Gasmischungen auf heterogenen Oberflächen

Zusammenfassung Das multiple Integral, das die Adsorption von Gasmischungen auf heterogenen Oberflächen darstellt, wurde zu einem einfachen Integral transformiert, das zur Voraussage der Adsorption von Gasgemischen mittels der Einzelgas-Adsorptionsparameter geeignet sein sollte. Diese Transformation ist dann möglich, wenn die Adsorptionsenergien der Komponenten einem bestimmten Korrelationstyp angehören.